JP2022041827A - Thermoplastic resin film, adhesive film, cosmetic film, and cosmetic adhesive film - Google Patents

Abstract

To provide a film that has excellent processability, excellent handleability, excellent heat resistance, an excellent appearance suitable for the use, and excellent adhesion to a printed layer, an adhesive layer and the like.SOLUTION: A thermoplastic resin film has at least one crystal melting peak in a temperature range of 70°C or higher and 170°C or lower in differential scanning calorimetry, and also has a crystal melting peak in a temperature region of 200°C or higher, includes a surface layer containing a polymethylpentene-based resin 0-20 mass% in a thermoplastic resin 100 mass%, and includes a layer including a polymethylpentene-based resin 20-90 mass% in the thermoplastic resin 100 mass%.SELECTED DRAWING: None

Description

The present invention relates to adhesive films (tapes) used in semiconductor manufacturing processes, cosmetic adhesive films (tapes) such as stickers, labels and marking films attached to impart design to automobiles and the like, and cosmetics. The present invention relates to a thermoplastic resin film preferably used as a base material such as a sheet, an adhesive film in which an adhesive layer is laminated on the film, a decorative film in which a printing layer is laminated, and the like.

Adhesive films (tapes), signs, cosmetic adhesive films (tapes) such as labels and marking films, decorative sheets, etc. that are conventionally attached to impart design to automobiles, etc. used in the semiconductor manufacturing process. A film made of a polyvinyl chloride resin (hereinafter, also referred to as "PVC-based film") having excellent colorability, processability, scratch resistance, weather resistance and the like has been widely used as a base material.
The PVC-based film has rigidity by itself, but a plasticizer is added for the purpose of imparting flexibility so that it can function as an adhesive film. However, depending on the plasticizer used, there are problems that the compatibility with the pressure-sensitive adhesive is poor, the stability is poor when the pressure-sensitive adhesive film is used, and the bleed-out of the plasticizer becomes remarkable. There is also a tendency for regulations to be tightened on the use of plasticizers themselves.
Therefore, a polyolefin-based resin film has been widely used as a material in place of the PVC-based film.

Decorative films for interior and exterior of buildings using polyolefin resin film as a base material, marking films for interior and exterior of automobiles, etc. are known. Film technology and the like are disclosed.
The general polyolefin-based resins described in these documents, such as polypropylene and polyethylene, do not have a melting point exceeding 200 ° C. and are not suitable as resins that can withstand high temperatures in the vicinity of 200 ° C. It is extremely difficult to form a film using a resin obtained by cross-linking them.

As a polyolefin resin having a melting point of 200 ° C. or higher, there is a polymethylpentene resin, and a technique relating to a film using the resin is already known, and it has been confirmed that the resin is used depending on the application (Patent Document). 3).
Further, there is also a technique of mixing a polymethylpentene-based resin with a general polyolefin-based resin such as polypropylene or polyethylene to form a film (Patent Document 4).

However, since the polymethylpentene-based resin is used alone in the technique described in Patent Document 3, it is presumed that it is difficult to process the polymethylpentene-based resin at a temperature equal to or lower than the melting point.
Further, in the technique described in Patent Document 4, since the layer containing polymethylpentene is only the skin layer and the content of the polymethylpentene-based resin used is small, heat resistance of the film at around 200 ° C. is imparted. It is considered insufficient for this.
Further, in the techniques described in Patent Document 3 and Patent Document 4, since the polymethylpentene-based resin is contained in the surface on which the print layer and the adhesive layer are laminated, when those layers are laminated on the film, those layers are added. There is a problem that the adhesion between the film and the laminated film is poor.

Further, as a heat-resistant polyolefin resin, there is also a technique of a polyolefin-based resin film using a polyamide-grafted polyolefin-based resin graft-bonded with polyamide (Patent Document 5).
However, in the technique described in Patent Document 5, foreign matter and streak-like appearance defects are observed, probably because the compatibility between the polyolefin-based resin and the polyamide-grafted polyolefin-based resin is not sufficient. There was room for improvement in the development of applications that require appearance management, such as automobile interior and exterior applications.

Therefore, it is improved to provide a film that solves these problems, such as good processability, handleability, heat resistance, excellent appearance according to the application, and adhesion to a printing layer, an adhesive layer, etc. It is considered that there is still room for this.

Japanese Unexamined Patent Publication No. 10-36590 Japanese Unexamined Patent Publication No. 11-172017 Japanese Unexamined Patent Publication No. 2012-228828 Japanese Patent No. 5816178 Japanese Patent No. 6535508

The present invention has been made in view of such conventional problems, and by using the thermoplastic resin film of the present invention, the film has good processability, handleability, heat resistance, excellent appearance according to the application, and It is possible to obtain a film that solves these problems, such as imparting adhesion to a printing layer, an adhesive layer, or the like. Further, it is also possible to obtain an adhesive film, a decorative film or a cosmetic adhesive film by laminating an adhesive layer or a printing layer on the film, and these films can be used for semiconductor manufacturing processes, automobile interior / exterior and automobile cosmetic applications. Can also be suitably used.

The present inventors have diligently studied thermoplastic resin films having good processability, handleability, heat resistance, excellent appearance according to the application, and adhesion to a printing layer, an adhesive layer, etc. We have found a thermoplastic resin film that can achieve both of these requirements, and have completed the present invention.

That is, the gist of the present invention is as follows.
[1]
In differential scanning calorimetry, it has at least one crystal melting peak in the temperature range of 70 ° C. or higher and 170 ° C. or lower, and further has a crystal melting peak in the temperature range of 200 ° C. or higher, in 100% by mass of the thermoplastic resin. It is characterized by having a surface layer containing 0 to 20% by mass of the polymethylpentene resin and having a layer containing 20 to 90% by mass of the polymethylpentene resin in 100% by mass of the thermoplastic resin. Thermoplastic resin film.
[2]
The thermoplastic resin film according to [1], which has a tensile elastic modulus of 1400 MPa or less.
[3]
The thermoplastic resin film according to [1] or [2], which comprises a thermoplastic resin having at least one crystal melting peak in the temperature range of 70 ° C. or higher and 150 ° C. or lower in the differential scanning calorimetry.
[4]
Item 2. The thermoplastic resin according to any one of [1] to [3], wherein any one or more of a polyolefin resin and a styrene elastomer is used as the thermoplastic resin other than the polymethylpentene resin. the film.
[5]
The thermoplastic resin film according to [4], wherein the polyolefin-based resin contains at least one selected from the group consisting of polypropylene-based resins and olefin-based elastomers.
[6]
The item according to any one of [1] to [5], wherein the film exhibits an elongation of 1500 μm in the range of 80 to 165 ° C. when thermomechanical analysis is performed under the following conditions. Thermoplastic resin film.
<Conditions>
Specimen size: width 4 mm x length 20 mm
Distance between chucks: 8 mm
Measurement atmosphere: Under nitrogen atmosphere (nitrogen flow rate 100 ml / min)
Temperature rise rate: 5 ° C / min (start temperature: 23 ° C, end temperature: 250 ° C)
Load: 0.3N / mm ²
[7]
The thermoplastic resin film according to any one of [1] to [6], wherein the storage elastic modulus E'at a vibration frequency of 1 Hz and a temperature of 190 ° C. is 1.0 × ¹⁰⁵ Pa or more.
[8]
The thermoplastic resin film according to any one of [1] to [7], wherein the surface layer has a thickness of 2.0 μm or more.
[9]
An adhesive film obtained by laminating an adhesive layer on the surface of the thermoplastic resin film according to any one of [1] to [8].
[10]
The adhesive film according to [9], which is used as a film for a semiconductor manufacturing process.
[11]
A decorative film formed by laminating a printing layer on the surface of the thermoplastic resin film according to any one of [1] to [8].
[12]
A cosmetic adhesive film obtained by further laminating an adhesive layer on the print layer side of the decorative film according to [11].

By using the thermoplastic resin film of the present invention, it is possible to obtain a film having good processability, handleability, heat resistance, excellent appearance according to the application, and adhesion to a printing layer, an adhesive layer, etc. Can be done. Further, it is also possible to obtain an adhesive film, a decorative film or a cosmetic adhesive film by laminating an adhesive layer or a printing layer on the film, and these films can be used for semiconductor manufacturing processes, automobile interior / exterior and their cosmetic applications. Can also be suitably used.

The present invention will be described in detail below, but the present invention is not limited to the following embodiments, and can be variously modified and carried out within the scope of the gist thereof. In addition, when the expression "-" is used in this specification, it shall be used as an expression including numerical values or physical property values before and after the expression.

One embodiment of the present invention has at least one crystal melting peak in the temperature range of 70 ° C. or higher and 170 ° C. or lower in differential scanning calorimetry, and further has a crystal melting peak in the temperature range of 200 ° C. or higher. It has a surface layer containing 0 to 20% by mass of the polymethylpentene resin in 100% by mass of the thermoplastic resin, and contains 20 to 90% by mass of the polymethylpentene resin in 100% by mass of the thermoplastic resin. It is a thermoplastic resin film characterized by having a layer (hereinafter, also referred to as “the thermoplastic resin film of the present invention”).

<Thermoplastic resin>
The resin composition used for producing the film of the present invention contains a thermoplastic resin as an essential component. Polyolefin-based resins are preferably used as thermoplastic resin components from the viewpoints of easy availability, flexibility, handleability, economy, and having an appropriate crystal melting peak.

Examples of the polyolefin resin include polyethylene resin, polypropylene resin, olefin elastomer, cyclic olefin resin, polymethylpentene resin and the like.
Among the polyolefin-based resins, polyethylene-based resins, polypropylene-based resins, and olefin-based elastomers are preferable from the viewpoint of easy availability and imparting flexibility to the obtained film.

Examples of the polyethylene-based resin include homopolymers of ethylene, copolymers of ethylene containing ethylene as a main component and other monomers copolymerizable (low density polyethylene (LDPE), high pressure method low density polyethylene, and the like. Linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE), ethylene-based copolymer (metallocene-based polyethylene) obtained by polymerization using a metallocene-based catalyst, ethylene-vinyl acetate copolymer, ethylene- (meth). ) Methyl acrylate copolymer, ethylene- (meth) ethyl acrylate copolymer, ethylene- (meth) butyl acrylate copolymer, ethylene- (meth) acrylate copolymer, ethylene- (meth) acrylic acid Examples thereof include a metal ion cross-linking resin (ionomer) of a copolymer.
Among them, low density polyethylene (LDPE) and linear low density polyethylene (LLDPE) are preferably used from the viewpoint of easy availability, handleability of the resin, and imparting flexibility to the obtained film.

Examples of the polypropylene-based resin include a homopolymer of propylene (homopolypropylene), a copolymer of propylene containing propylene as a main component and another monomer copolymerizable with the copolymer, and a mixture thereof.
Examples of the copolymer of propylene containing propylene as a main component and a copolymerizable other monomer include a random copolymer (random polypropylene) of propylene and ethylene or another α-olefin, or a block copolymer. (Block polypropylene), a block copolymer containing a rubber component, a graft copolymer and the like can be mentioned.
The α-olefin used as another monomer copolymerizable with propylene is preferably one having 4 to 12 carbon atoms, and is, for example, 1-butene, 1-pentene, 1-hexene, 1-hexene. , 1-octene, 4-methyl-1-pentene, 1-decene and the like, and one or a mixture of two or more thereof is used.
Among these, it is preferable to use a random copolymer (random polypropylene) and / or a homopolymer (homopolypropylene) from the viewpoint of controlling heat resistance and easy availability.

The olefin-based elastomer is a soft resin containing a polyolefin-based resin and a rubber component, and the rubber component may be dispersed in the polyolefin-based resin or may be copolymerized with each other.
Specific examples of the olefin-based elastomer include, for example, ethylene-propylene copolymer elastomer, ethylene-1-butene copolymer elastomer, ethylene-propylene-1-butene copolymer elastomer, and ethylene-1-hexene copolymer elastomer. , Ethylene-1-octene copolymer elastomer, ethylene-styrene copolymer elastomer, ethylene-norbornen copolymer elastomer, propylene-1-butene copolymer elastomer, ethylene-propylene-non-conjugated diene copolymer elastomer, ethylene Atypical elastic copolymers mainly composed of olefins such as -1-butene-non-conjugated diene copolymer elastomer and ethylene-propylene-1-butene-non-conjugated diene copolymer elastomer, derivatives thereof and acid modification. Derivatives and the like can be mentioned.

The above-mentioned polyethylene-based resin, polypropylene-based resin, olefin-based elastomer and the like may be used alone or in combination of two or more. From the viewpoint of the flexibility of the obtained film and the film-forming property when processing the film, it is preferable to use two or more kinds in combination.
Further, from the viewpoint of compatibility with the polymethylpentene resin described later, it is preferable to use either a polypropylene resin or an olefin elastomer, and they may be used alone or in combination of the two. good.

The melt flow rate of the polyolefin resin such as the polyethylene resin, polypropylene resin, and olefin elastomer described above is appropriately selected depending on the molding method and application to which it is applied, but is loaded under a temperature condition of 190 ° C or 230 ° C. The value measured at .16 kg is preferably 0.1 to 50 g / 10 minutes. When it is 0.1 g / 10 minutes or more, the formability of the obtained film becomes good, and when it is 50 g / 10 minutes or less, the thickness accuracy of the obtained film can be kept good. It is more preferably 0.5 to 40 g / 10 minutes, still more preferably 1.0 to 30 g / 10 minutes.

The crystal melting peak of a polyolefin resin such as a polyethylene resin, a polypropylene resin, and an olefin elastomer is preferably in the range of 70 ° C. or higher and 170 ° C. or lower as a value measured by differential scanning calorimetry. By having the crystal melting peak in the range of 70 ° C. or higher and 170 ° C. or lower, it is possible to improve the processability of the obtained film at a temperature of 200 ° C. or lower. It is more preferably 72 ° C. or higher and 168 ° C. or lower, and further preferably 75 ° C. or higher and 165 ° C. or lower. Further, by using a material having a crystal melting peak in the range of 70 ° C. or higher and 150 ° C. or lower, it is possible to further improve the processability of the film at a temperature of 200 ° C. or lower.
Here, as a condition for measuring the differential scanning calorimetry, the temperature is usually raised from 25 ° C. to 250 ° C. at a heating rate of 10 ° C./min, then lowered to 25 ° C. at a cooling rate of 10 ° C./min, and then raised again. The temperature is raised to 250 ° C. at a speed of 10 ° C./min.

Regarding the strength of polyolefin-based resins such as polyethylene-based resins, polypropylene-based resins, and olefin-based elastomers, the tensile elastic modulus of the film obtained by these resins alone is preferably in the range of 100 to 2000 MPa. When the tensile elastic modulus is in the range of 100 to 2000 MPa, it is possible to impart appropriate flexibility to the film of the present invention.
It is more preferably in the range of 150 to 1900 MPa, still more preferably in the range of 200 to 1800 MPa.

The content of the polyolefin-based resin such as the polyethylene-based resin, the polypropylene-based resin, and the olefin-based elastomer can be appropriately selected depending on the content of the polymethylpentene-based resin described later.

The thermoplastic resin film of the present invention has a crystal melting peak of 200 ° C. or higher for the purpose of imparting a crystal melting peak of 200 ° C. or higher, and is described above from the viewpoint of compatibility with the various polyolefin resins described above. It is preferable to add a polymethylpentene resin in addition to the polyolefin resin. The polymethylpentene-based resin means a homopolymer having methylpentene as a monomer or a copolymer with other monomers. Specific examples include a copolymer of 4-methylpentene-1 and an α-olefin exemplified as another monomer copolymerizable with propylene.

When the polymethylpentene-based resin is a copolymer, the content of the α-olefin component used for the copolymerization is preferably 20% by mass or less. By setting the content to 20% by mass or less, it is possible to suppress a decrease in the crystal melting peak. More preferably, it is 10% by mass or less.

The melt flow rate of the polymethylpentene resin is appropriately selected depending on the molding method and application to which it is applied, but the value measured under a temperature condition of 260 ° C. under a load of 5.0 kg is 0.1 to 50 g / 10 minutes. It is preferable to have. When it is 0.1 g / 10 minutes or more, the formability of the film is good, and when it is 50 g / 10 minutes or less, the thickness accuracy of the film can be kept good. It is more preferably 0.5 to 40 g / 10 minutes, still more preferably 1.0 to 35 g / 10 minutes.

The crystal melting peak of the polymethylpentene resin preferably shows 210 ° C. or higher as a value measured by differential scanning calorimetry. Having a crystal melting peak of 210 ° C. or higher makes it possible to sufficiently impart heat resistance to the obtained film. It is more preferably 215 ° C. or higher, still more preferably 220 ° C. or higher.
Here, as the conditions for measuring the differential scanning calorimetry, the same method as described above can be used.

Regarding the strength of the polymethylpentene-based resin, it is preferable that the tensile elastic modulus of the film obtained by the resin alone is in the range of 100 to 2000 MPa. When the tensile elastic modulus is in the range of 100 to 2000 MPa, it is possible to impart appropriate flexibility to the film of the present invention. It is more preferably in the range of 150 to 1900 MPa, still more preferably in the range of 200 to 1800 MPa.

Since the content of the polymethylpentene resin differs between the surface layer of the obtained film and each layer of the other layers, it will be described in detail in the section of the thermoplastic resin film described later.

The resin composition used for the thermoplastic resin film of the present invention may be a resin other than the above-mentioned polyethylene-based resin, polypropylene-based resin, olefin-based elastomer and other polyolefin-based resins and polymethylpentene-based resin, if necessary. A styrene-based elastomer, a cyclic olefin-based resin, or the like can also be added.

The styrene-based elastomer is preferably a block copolymer represented by the following formula (I) or (II).
X- (YX) n ... (I)
(XY) n ... (II)
X in the general formulas (I) and (II) is an aromatic vinyl polymer block typified by styrene, and in the formula (I), the degree of polymerization may be the same or different at both ends of the molecular chain. May be good. In addition, Y is a butadiene polymer block, an isoprene polymer block, a butadiene / isoprene copolymer block, a hydrogenated butadiene polymer block, a hydrogenated isoprene polymer block, and a hydrogenated butadiene / isoprene co-weight. At least one selected from coalesced blocks, partially hydrogenated butadiene polymer blocks, partially hydrogenated isoprene polymer blocks and partially hydrogenated butadiene / isoprene copolymer blocks. Further, n is an integer of 1 or more.

Specific examples of the styrene-based elastomer include styrene-ethylene / butylene-styrene copolymer, styrene-ethylene / propylene-styrene copolymer, styrene-ethylene / ethylene / propylene-styrene copolymer, and styrene-butadiene-butene-. Styrene copolymer, styrene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, styrene-hydrogenated butadienediblock copolymer, styrene-hydrogenated isoprange block copolymer, styrene-butadienediblock Examples thereof include copolymers, styrene-isopregen block copolymers, etc. Among them, styrene-ethylene / butylene-styrene copolymers, styrene-ethylene / propylene-styrene copolymers, styrene-ethylene / ethylene / propylene-styrene. A copolymer and a styrene-butadiene-butene-styrene copolymer are suitable. Further, a block copolymer which is a styrene-ethylene / butylene-crystalline olefin copolymer can also be used.
The melt flow rate of the styrene-based elastomer (value measured under a temperature condition of 230 ° C. and a load of 2.16 kg) is preferably 0.1 to 10 g / 10 minutes, preferably 0.15 to 9 g / 10 minutes. It is more preferable, and 0.2 to 8 g / 10 minutes is particularly preferable. When the melt flow rate of the styrene-based elastomer is less than 0.1 g / 10 minutes and exceeds 10 g / 10 minutes, sufficient flexibility and expandability are exhibited due to the decrease in compatibility with the polyolefin-based resin and the deterioration of film-forming property. It may not be.

Commercially available styrene-based elastomers include, for example, Toughprene A, Toughprene 125, Asaplen T-438, Asaplen T-439, Toughtech H1221, Toughtech H1041, Toughtech H1052, Toughtech H1053, Toughtech H1517 (all manufactured by Asahi Kasei), Septon. 4099, Septon HG252, Septon 8004, Septon 8006, Septon 8007L, Septon HG252, Septon V9461 , Dynaron 8903P, Dynaron 9901P (all manufactured by JSR Corporation) and the like.

As the styrene-based elastomer, one type of elastomer may be used alone, or two or more types may be used in combination. It can be appropriately selected as necessary in consideration of the film-forming property when obtaining the multi-layer film, the flexibility and handleability of the obtained multi-layer film, and the expandability. From the viewpoint of the film-forming property of the multi-layer film and the performance of the obtained film, it is more preferable to use two or more types in combination.

Examples of the cyclic olefin-based resin include norbornene-based polymers, vinyl alicyclic hydrocarbon polymers, and cyclic conjugated diene polymers. Among these, norbornene-based polymers are preferable. Examples of the norbornene-based polymer include a ring-opening polymer of a norbornene-based monomer, a norbornene-based copolymer obtained by copolymerizing a norbornene-based monomer and an α-olefin such as ethylene. Moreover, these hydrogenated additives can also be used.

When a styrene-based elastomer or a cyclic olefin-based resin is added to the resin composition used for the thermoplastic resin film of the present invention, the content of the styrene-based elastomer and the cyclic olefin-based resin is the polyethylene-based resin, the polypropylene-based resin, and the olefin. It can be appropriately selected depending on the content of the polyolefin resin such as the system elastomer and the content of the polymethylpentene resin.

<Other ingredients>
In the resin composition used for the thermoplastic resin film of the present invention, various additives are added in order to impart heat resistance, weather resistance, etc. in addition to the thermoplastic resin components such as the above-mentioned polyolefin resin and polymethylpentene resin. Can be blended.
Specific examples include, for example, antistatic agents, antioxidants, neutralizers, lubricants, antiblocking agents, plasticizers, heat stabilizers, light stabilizers, dyes and pigments, crystal nucleating agents, ultraviolet absorbers, fillers, etc. Inorganic fillers that impart rigidity, elastomers other than those described above for imparting flexibility, and the like may be used as long as the effects of the present invention are not impaired.

As the ultraviolet absorber, known ones can be used, and examples thereof include a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, and a triazine-based ultraviolet absorber.
As the light stabilizer, known ones can be used, and examples thereof include hindered amine-based light stabilizers.
As the antistatic agent, known ones can be used, but a polymer type antistatic agent may be used in order to impart long-term antistatic properties to the film and suppress defects caused by bleeding out to the surface. preferable. As a specific example of the polymer antistatic agent, known ones can be used, for example, a block copolymer of a hydrophobic block and a hydrophilic block can be used, and a hydrophobic block and a hydrophilic block can be used. However, examples thereof include those in which a block copolymer is formed by an ester bond, an ether bond, an amide bond, an imide bond, a urethane bond, a urea bond, or the like.
As a lubricant or anti-blocking agent, it has excellent compatibility with the above-mentioned polyolefin resin, and it enables defects due to bleed-out to the surface of the obtained film and long-term scratch resistance and slipperiness. It is preferable to use a silicone-olefin copolymer.

<Thermoplastic resin film>
The thermoplastic resin film of the present invention has a surface layer containing 0 to 20% by mass of a polymethylpentene resin in 100% by mass of the thermoplastic resin, and the polymethylpentene resin in 100% by mass of the thermoplastic resin. It is a thermoplastic resin film characterized by having a layer containing 20 to 90% by mass of.

By using a layer containing 0 to 20% by mass of polymethylpentene resin in 100% by mass of the thermoplastic resin as the surface layer, a printing layer is used when a printing layer, an adhesive layer, or the like is laminated on the surface layer surface. And the adhesive layer and the film can be sufficiently adhered to each other. The content of the polymethylpentene resin contained in the surface layer can be appropriately selected from the viewpoints of the use of the film, heat resistance and economy, and more preferably 0 to 15% by mass in 100% by mass of the thermoplastic resin. Within the range, more preferably in the range of 0 to 10% by mass in 100% by mass of the thermoplastic resin, and in the surface layer, the polymethylpentene resin is an optional component.
Here, the above-mentioned "100% by mass of the thermoplastic resin" means the thermoplastic resin contained in the surface layer (that is, a component of the thermoplastic resin other than the polymethylpentene resin described in detail in the previous section) and the polymethylpentene resin. It means that the total content of is 100% by mass.

The thermoplastic resin composition used for the surface layer preferably contains at least one of a polyolefin resin and a styrene elastomer as a thermoplastic resin other than the polymethylpentene resin.
Here, as the polyolefin-based resin other than the polymethylpentene-based resin, a polyethylene-based resin, a polypropylene-based resin, an olefin-based elastomer, or a cyclic olefin-based resin described in detail in the previous section can be used, and a polyethylene-based resin is preferable. , One or more selected from the group consisting of polypropylene-based resin and olefin-based elastomer is used, and more preferably any one or more selected from the group consisting of polypropylene-based resin and olefin-based elastomer is used. Used. These polyolefin-based resins may be used alone or in combination of two or more.
Further, as the styrene-based elastomer, those described in detail in the preceding section may be used alone, or two or more kinds may be used in combination.

When the thermoplastic resin composition used for the surface layer contains a polyolefin-based resin and a styrene-based elastomer as a thermoplastic resin other than the polymethylpentene-based resin, the content of both is the content of the polyolefin-based resin and the styrene-based elastomer. It is preferably 100: 0 to 50:50 (= polyolefin-based resin: styrene-based elastomer) with respect to the total amount.
By setting the content of the styrene-based elastomer in the thermoplastic resin other than the polymethylpentene-based resin used for the surface layer to 0% by mass or more and 50% by mass or less, the multi-layer film is given flexibility and the styrene-based elastomer is used. It is possible to suppress the tackiness of the film surface layer due to the above, suppress the sticking of the film to a roll or the like when producing a multilayer film, and improve the process passability.
The range of the content ratio is more preferably 100: 0 to 55:45, and even more preferably 100: 0 to 60:40 (= polyolefin resin: styrene elastomer).

Further, in the thermoplastic resin film of the present invention, it is important to provide a layer (hereinafter, also referred to as “layer A”) containing 20 to 90% by mass of the polymethylpentene resin in 100% by mass of the thermoplastic resin. .. By providing such a layer, heat resistance and excellent appearance can be imparted to the obtained film. By setting the polymethylpentene resin to 20% by mass or more in 100% by mass of the thermoplastic resin, it is possible to impart sufficient heat resistance to the obtained film, and by setting it to 90% by mass or less, the appearance of the film It is possible to suppress the deterioration of the above, which is preferable. The content of the polymethylpentene resin is more preferably 22 to 68% by mass in 100% by mass of the thermoplastic resin, and further preferably 25 to 65% by mass in 100% by mass of the thermoplastic resin. Further, the layer containing 20 to 90% by mass of the polymethylpentene resin in 100% by mass of the thermoplastic resin may be composed of a single layer or a plurality of layers, and when the layer is composed of a plurality of layers, each layer may be composed of a single layer or a plurality of layers. The composition of the above may be the same or different.
Here, the above-mentioned "100% by mass of thermoplastic resin" means the polyolefin-based resin contained in the above-mentioned layer A (that is, the component of the thermoplastic resin other than the polymethylpentene-based resin detailed in the previous section) and polymethyl. It means that the total content of the penten-based resin is 100% by mass.

The thermoplastic resin composition used for the layer A preferably contains at least one of a polyolefin resin and a styrene elastomer as a thermoplastic resin other than the polymethylpentene resin.
That is, the thermoplastic resin composition used for the layer A preferably contains, as resin components, (1) polymethylpentene-based resin and polyolefin-based resin, (2) polymethylpentene-based resin and styrene-based elastomer, and (3) poly. Contains methylpentene-based resin, polyolefin-based resin and styrene-based elastomer.
Here, as the polyolefin resin other than the polymethylpentene resin, a polyethylene resin, a polypropylene resin, an olefin elastomer, a cyclic olefin resin can be used, and a polyethylene resin, a polypropylene resin, and a polypropylene resin are preferable. Any one or more selected from the group consisting of olefin-based elastomers is used, and more preferably any one or more selected from the group consisting of polypropylene-based resins and olefin-based elastomers is used. These polyolefin-based resins may be used alone or in combination of two or more.
Further, as the styrene-based elastomer, those described in detail in the preceding section may be used alone, or two or more kinds may be used in combination.

When the thermoplastic resin composition used for layer A contains a polyolefin-based resin and a styrene-based elastomer as a thermoplastic resin other than the polymethylpentene-based resin, the content of both is the same as that of the polyolefin-based resin and the styrene-based elastomer. It is preferably 100: 0 to 20:80 (= polyolefin-based resin: styrene-based elastomer) with respect to the total content.
By setting the content of the styrene-based elastomer in the thermoplastic resin other than the polymethylpentene-based resin used for the layer A to 0% by mass or more and 80% by mass or less, the resulting multi-layer film is flexible without impairing the heat resistance. It is possible to impart sex.
The range of the content ratio is more preferably 100: 0 to 25:75, and even more preferably 100: 0 to 30:70 (= polyolefin resin: styrene elastomer).

In the thermoplastic resin film of the present invention, a layer containing 20 to 90% by mass of a polymethylpentene resin in 100% by mass of the thermoplastic resin is used as an intermediate layer, and a back layer is provided on a surface opposite to the surface layer. You may. By imparting a back layer, it is easy to impart necessary performance such as heat resistance and weather resistance to the film. Further, the back layer may have the same composition as the intermediate layer or the surface layer, may have a different composition, or may be composed of a single layer or a plurality of layers.
The details of the thermoplastic resin composition used for the back layer are the same as those described in detail above for the thermoplastic resin composition used for the surface layer and the thermoplastic resin composition used for the intermediate layer (layer A).

The thermoplastic resin film of the present invention has at least one crystal melting peak in the temperature range of 70 ° C. or higher and 170 ° C. or lower in differential scanning calorimetry, and further has a crystal melting peak in the temperature range of 200 ° C. or higher. This is very important.
Having a crystal melting peak in the range of 70 ° C. or higher and 170 ° C. or lower makes it possible to improve processability at a temperature of 200 ° C. or lower. It is more preferably 70 ° C. or higher and 160 ° C. or lower, and further preferably 70 ° C. or higher and 150 ° C. or lower.
Here, as the conditions for measuring the differential scanning calorimetry, the same method as described above can be used.

The thermoplastic resin film of the present invention uses a test piece collected using a dumbbell "SDK-600" prepared according to JIS K6732, and has the following conditions with reference to JIS K7127; 23 ° C., 50% RH. It is preferable that the tensile elastic modulus is 1400 MPa or less when measured at a tensile speed of 50 mm / min with a tensile tester under an atmosphere.
By setting the pressure to 1400 MPa or less, the processability when laminating the printing layer and the pressure-sensitive adhesive layer on the thermoplastic resin film of the present invention and the thermoplastic resin film of the present invention having the pressure-sensitive adhesive layer have a three-dimensional shape such as an automobile exterior. It is possible to maintain good handleability and workability in the process of bonding to an article having a resin, and handleability in the semiconductor manufacturing process. It is more preferably 1350 MPa or less, still more preferably 1300 MPa or less. The tensile elastic modulus of the obtained thermoplastic resin film can be adjusted by adjusting the type and addition amount of the thermoplastic resin described above, and changing the film forming method and molding conditions described later.

As a method for forming the thermoplastic resin film of the present invention, a known method can be used, but it is preferable to use a melt extrusion molding method. Among the melt extrusion molding methods, the T-die molding method in which a resin in a molten state is extruded from an extruder having a T-die and cooled and solidified to obtain a film is more preferable.
In order to obtain a film, it is preferable to use a coextrusion T-die molding method using a plurality of extruders. A multi-layer film can be obtained by using a co-extrusion T-die molding method using a plurality of extruders, and a single-layer film can be obtained by extruding the same resin from all the extruders. It is also possible.
As a coextrusion T-die molding method, a method of forming a plurality of resin layers into a film by using a multi-manifold die and then contacting the resin layers in the T-die to form a multi-layer to obtain a film, and a melting method called a feed block. Examples thereof include a method of obtaining a multi-layer film after merging and adhering a plurality of resins using a device for merging the resins in the state.

If necessary, the film may be surface-treated on one or both sides by a method such as plasma treatment, corona treatment, ozone treatment, and flame treatment. Depending on the application of the obtained film, it is possible to select whether to perform surface treatment on one side or both sides.

The thickness of the thermoplastic resin film of the present invention is not particularly limited, but is preferably 30 to 400 μm. Within the above range, the handleability of the film and the subsequent processability can be maintained satisfactorily. It is more preferably 50 to 350 μm, still more preferably 70 to 300 μm.

Further, in the thermoplastic resin film of the present invention, the thickness of the surface layer is preferably in the range of 5 to 40% of the total thickness. When it is 5% or more, it is possible to fully express the performance of the additive when various additives are added to the surface layer, and when it is 40% or less, the film-forming property when obtaining a multi-layer film is obtained. It is preferable because it is possible to maintain good economic efficiency. It is more preferably in the range of 5 to 35%, still more preferably in the range of 5 to 30%.

As the breaking elongation of the thermoplastic resin film of the present invention, a test piece collected using a dumbbell "SDK-600" prepared according to JIS K6732 was used, and the following conditions with reference to JIS K7127, 23 ° C., It is preferable that the tensile elongation at break when measured at a tensile speed of 300 mm / min with a tensile tester under an atmosphere of 50% RH is 150% or more. If the tensile elongation at break is 150% or more, defects due to film breakage during melt extrusion molding and similar defects in the subsequent step of laminating the printing layer and the pressure-sensitive adhesive layer are suppressed. It is preferable because it can be used. It is more preferably 250% or more, still more preferably 350% or more.

It is preferable that the thermoplastic resin film of the present invention exhibits an elongation of 1500 μm in the range of 80 to 165 ° C. when subjected to thermomechanical analysis under the following conditions.

<Conditions>
Specimen size: width 4 mm x length 20 mm
Distance between chucks: 8 mm
Measurement atmosphere: Under nitrogen atmosphere (nitrogen flow rate 100 ml / min)
Temperature rise rate: 5 ° C / min (start temperature: 23 ° C, end temperature: 250 ° C)
Load: 0.3N / mm ²

By exhibiting an elongation of 1500 μm in the range of 80 to 165 ° C., when the film is made into an adhesive film, the followability to the adherend in the step of heating the film and adhering it to the adherend is improved. It becomes possible. It is more preferably in the range of 90 to 165 ° C, still more preferably in the range of 100 to 165 ° C.

Further, it is preferable that the thermoplastic resin film of the present invention has a storage elastic modulus of 1.0 × ¹⁰⁵ Pa or more at 190 ° C. When the storage elastic modulus is 1.0 × ¹⁰⁵ Pa or more, the shape of the film can be maintained without being completely melted in the step of heating the film and attaching it to the adherend when the film is used as an adhesive film. Therefore, it is possible to maintain good handleability and process passability. It is more preferably 2.0 × 10 ⁵ Pa or more, and further preferably 3.0 × 10 ⁵ Pa or more.

<Adhesive film>
The thermoplastic resin film of the present invention can be made into an adhesive film by laminating an adhesive layer on the surface layer (hereinafter, also referred to as "adhesive film of the present invention").
The pressure-sensitive adhesive used as the pressure-sensitive adhesive layer is not particularly limited, and for example, various pressure-sensitive adhesives such as natural rubber-based resin, acrylic-based resin, styrene-based resin, silicon-based resin, and polyvinyl ether-based resin are used. Further, a functional layer such as an adhesive layer or a thermosetting resin layer may be further provided on the pressure-sensitive adhesive layer.

In the pressure-sensitive adhesive film of the present invention, one or both sides of the film before laminating the pressure-sensitive adhesive layer may be subjected to the above-mentioned surface treatment. Further, a primer layer may be provided between the base film, which is the thermoplastic resin film of the present invention, and the pressure-sensitive adhesive layer, if necessary.
The thickness of the pressure-sensitive adhesive layer and the primer layer can be appropriately determined as needed.

<Cosmetic film>
The thermoplastic resin film of the present invention can be formed into a decorative film by laminating a printing layer on the surface layer (hereinafter, also referred to as “decorative film of the present invention”).
The print layer constituting the decorative film can be formed by a known method. For example, a known printing method such as an offset printing method, a gravure rotary printing method, and a screen printing method, a known coating method such as a roll coating method and a spray coating method, a flexographic printing method, and the like can be mentioned. Further, a thin-film deposition method can also be used.
Examples of the printed pattern include a pattern consisting of wood grain, stone grain, cloth grain, sand grain, geometric pattern, characters, solid surface, metallic, and the like.
The thickness of the print layer can be appropriately determined as needed.
In the decorative film of the present invention, the above-mentioned surface treatment may be applied to one or both sides of the film before laminating the print layer. Further, a primer layer may be provided between the base film and the printing layer, if necessary.
The thickness of the print layer and the primer layer can be appropriately determined as needed.

<Adhesive film for cosmetics>
The decorative film of the present invention can be made into a cosmetic adhesive film by further laminating a pressure-sensitive adhesive layer on the printed layer, if necessary.
By attaching the cosmetic adhesive film to the adherend, it is possible to give a beautiful appearance to the adherend, and it is possible to give a beautiful appearance to the adherend, and it is used for cosmetics for interior and exterior of automobiles, other molded bodies and laminates, and applications for interior and exterior of buildings. It can be used for such purposes.

The thermoplastic resin film of the present invention has good processability, handleability, heat resistance, excellent appearance according to the application, and adhesion to a printing layer, an adhesive layer, or the like. Further, it is also possible to obtain an adhesive film or a decorative film by laminating an adhesive layer or a printing layer on the film, and these films can be suitably used for various applications such as automobile cosmetics and semiconductor manufacturing processes. Can be done.

Hereinafter, examples and comparative examples of the present invention will be shown and specifically described, but the present invention is not limited to these examples. The materials used in the following examples and comparative examples, the method for measuring the evaluated characteristics, and the like are as follows.

[Material used]
<Thermoplastic resin>
<Polyolefin resin>
Polymethylpentene (A):
Mitsui Chemicals, Inc .: "RT18" (polymethylpentene resin, melt flow rate at 260 ° C., 5.0 kg: 26 g / 10 minutes, melting point: 232 ° C., tensile elastic modulus of a single film: 1640 MPa)
Polymethylpentene (B):
Mitsui Chemicals, Inc .: "MX002" (polymethylpentene resin, melt flow rate at 260 ° C., 5.0 kg: 21 g / 10 minutes, melting point: 224 ° C., tensile elastic modulus of a single film: 1110 MPa)
Random polypropylene:
"PC630A" manufactured by Japan Polypropylene Corporation (random polypropylene, 230 ° C., melt flow rate at 2.16 kg: 7.5 g / 10 minutes, melting point: 135 ° C., tensile elastic modulus of a single film: 500 MPa)
Homopolypropylene:
"FY6HA" manufactured by Japan Polypropylene Corporation (homopolypropylene, melt flow rate at 230 ° C., 2.16 kg: 2.4 g / 10 minutes, melting point: 169 ° C., tensile modulus of elasticity of a single film: 900 MPa)
Olefin elastomer:
"Wellnex RFX4V" manufactured by Japan Polypropylene Corporation (olefin elastomer, melt flow rate at 230 ° C., 2.16 kg: 6.0 g / 10 minutes, melting point: 127 ° C., tensile modulus of elasticity of a single film: 250 MPa)
Polyamide grafted polyolefin resin:
"Apollya LP21H" manufactured by Arkema (polyamide grafted polyolefin resin, melt flow rate at 230 ° C., 2.16 kg: 10 g / 10 minutes, melting point: 216 ° C., tensile elastic modulus of a single film: 180 MPa)
<Styrene-based elastomer>
Styrene-based elastomer (A):
"Tough Tech H1221" manufactured by Asahi Kasei Corporation (melt flow rate at 230 ° C., 2.16 kg: 4.5 g / 10 minutes, styrene component content: 12% by mass, styrene-ethylene / butylene-styrene copolymer)
Styrene-based elastomer (B):
"Hybuler 7311" manufactured by Kuraray (melt flow rate at 230 ° C., 2.16 kg: 2.0 g / 10 minutes, styrene component content: 12% by mass, styrene-ethylene / ethylene / propylene-styrene copolymer)

<Preparation of resin composition>
Using the above-mentioned thermoplastic resin, the total amount of the thermoplastic resin components in each layer was set to 100% by mass based on the description in Table 1, and they were dry-blended and mixed. After visually confirming that the mixture was uniformly mixed, a resin composition for film molding was prepared.

<Method of forming a multi-layer film>
For each hopper of three Toshiba Machine single-screw extruders (for outer layer: 35φmm, L / D = 25mm, for intermediate layer: 50φmm, L / D = 32, for outer layer: 35φmm, L / D = 25mm) The dry-blended raw material is added, the extruder temperature for the surface layer, the intermediate layer, and the back layer is set to 210 to 265 ° C., and the feed block portion has a three-layer structure of surface layer / intermediate layer / back layer. They were merged and extruded from a 650 mm wide T-die (temperature setting 265 ° C. lip opening 0.5 mm). As for the thickness configuration, each extruder rotation speed was set so as to have the thickness shown in Table 1 (150 μm in total for each layer).
The extruded molten resin is cooled and solidified by a winder equipped with a mirror-shaped cooling roll (cooling roll 700 mm width x φ350 mm, roll temperature of about 30 ° C.), and then corona-treated on both sides to perform winding. A film composed of a resin layer of 2 types and 3 layers or a resin layer of 3 types and 3 layers having a thickness of about 150 μm was obtained.
Further, in the present invention, the surface on the cooling roll side is expressed as a surface layer.

[Appearance of film]
The appearance of the obtained film was visually evaluated using the following criteria.
◎: No foreign matter or streaks are found 〇: Foreign matter or streaks are slightly found △: Foreign matter or streaks are found ×: Foreign matter or streaks are noticeably confirmed and cannot be used

[Ink adhesion (α)]
The ink for olefin-based building material film manufactured by Dainichiseika Kogyo Co., Ltd. described below is used on the surface layer side of the film using a gravure printing tester "GP-2" and a printing plate "54L6 gradation" manufactured by Kurashiki Spinning Co., Ltd. The coating was performed. The coated film was aged at 40 ° C. for 5 days to obtain a decorative film on which a printing layer with ink was laminated.
Cellotape was attached to the printed layer of the obtained decorative film, and the adhesiveness between the printed layer and the thermoplastic resin film was evaluated according to the following criteria by peeling it off.
⊚: Ink of all 6 gradations remains and peeling is not recognized. 〇: Ink of 4 to 5 gradations remains and peeling of 1 to 2 gradations is recognized. Peeling of 3 to 4 gradations is observed. ×: The remaining ink is 1 gradation or less.

<Ink for olefin-based building material film manufactured by Dainichiseika Kogyo Co., Ltd.>
Using 100 parts by mass of "SBM-NT95 ink (M)" and 3 parts by mass of "PTC-LT curing agent (K)", they were mixed and stirred to prepare an ink.
"SBM-NT95 Ink (M)": Polyurethane-based resin, a solvent consisting of ketones / esters / alcohols, and a paint containing carbon black as a pigment "PTC-LT curing agent (K)": Curing agent for polyurethane-based resins

[Ink adhesion (β)]
The following ink for vinyl chloride decorative film manufactured by DIC Graphics Co., Ltd. was applied to the surface layer side of the film using a gravure printing tester "GP-2" and a printing plate "54L6 gradation" manufactured by Kurashiki Spinning Co., Ltd. The coating was performed. The coated film was aged at 40 ° C. for 5 days to obtain a decorative film on which a printing layer with ink was laminated.
Cellotape was attached to the printed layer of the obtained decorative film, and the adhesiveness between the printed layer and the thermoplastic resin film was evaluated according to the following criteria by peeling it off.
⊚: Ink of all 6 gradations remains and peeling is not recognized. 〇: Ink of 4 to 5 gradations remains and peeling of 1 to 2 gradations is recognized. Peeling of 3 to 4 gradations is observed. ×: The remaining ink is 1 gradation or less.

<Ink for PVC decorative film manufactured by DIC Graphics Co., Ltd.>
Using 95 parts by mass of "VTP-NT40 yellow (A)" and 5 parts by mass of "AT-NT solvent", they were mixed and stirred to prepare an ink.
"VTP-NT40 Yellow (A)": Paint consisting of a mixture of vinyl chloride / vinyl acetate copolymer and acrylic resin and methyl isobutyl ketone as a solvent "AT-NT solvent": Mixture of butyl acetate / ethyl acetate / methyl ethyl ketone

[Tension modulus]
From the obtained multi-layer film, a test piece was collected using a dumbbell "SDK-600" prepared according to JIS K6732, and the following conditions with reference to JIS K7127, 23 ° C., 50% RH atmosphere, auto. The tensile elastic modulus (MPa) was measured at a tensile speed of 50 mm / min using a graph (AGS-X manufactured by Shimadzu Corporation).
The tensile elastic modulus was measured in the extrusion direction (MD) of the film.

[Tension breaking elongation]
From the obtained film, a test piece was collected using a dumbbell "SDK-600" prepared according to JIS K6732, and under an atmosphere of 23 ° C. and 50% RH, a small tabletop tester (EZ-L manufactured by Shimadzu Corporation). ) Was used to measure the tensile elongation at break (%) at a tensile speed of 300 mm / min.
The tensile elongation at break was measured in the extrusion direction (MD) of the film.

[Crystal melting peak]
Using a differential scanning calorimetry device (DSC823e manufactured by METTLER TOLEDO), about 5 mg of the film obtained in each example was heated from 25 ° C. to 250 ° C. at a heating rate of 10 ° C./min, and then cooled. The crystal melting peak was calculated from the chart measured when the temperature was lowered to 25 ° C. at 10 ° C./min and the temperature was raised to 250 ° C. at a heating rate of 10 ° C./min again.

[Temperature at extension of 1500 μm]
The temperature of the 150 μm film at the time of extension of 1500 μm was measured using the following measuring devices and conditions.

<Measurement conditions>
Equipment: Thermomechanical analyzer TMA7100 (manufactured by Hitachi High-Tech Science Corporation)
Specimen size: width 4 mm x length 20 mm
Distance between chucks: 8 mm
Measurement atmosphere: Under nitrogen atmosphere (nitrogen flow rate 100 ml / min)
Temperature rise rate: 5 ° C / min (start temperature: 23 ° C, end temperature: 250 ° C)
Load: 0.3N / mm ²
[Storage modulus at 190 ° C. (E')]
Using a dynamic viscoelasticity measuring device (“DVA-200” manufactured by IT Measurement Control Co., Ltd.), the MD direction of the film is pulled by tension, the distance between chucks is 25 mm, the strain is 0.1%, the frequency is 1 Hz, and the temperature rises. The temperature range of −50 to 250 ° C. was measured under the condition of a speed of 3 ° C./min, and the storage elastic modulus (E') of the film at 190 ° C. was calculated.

[Example 1]
Polymethylpentene (A) and random polypropylene were used as the polyolefin resins used for the surface layer, the intermediate layer, and the back layer, and a film consisting of two types and three layers was obtained. The blending amounts of various thermoplastic resins are as shown in Table 1.
No foreign matter or streak-like defects were found in this film, and the film had an excellent appearance.
It was confirmed that the tensile elastic modulus was 870 MPa and the tensile elongation at break was 500%, and that it had sufficient flexibility and fracture characteristics.
Regarding the adhesion of the ink provided on the surface layer side of this film, in the case of the olefin-based building material film ink, no peeling was observed in all 6 gradations, showing excellent adhesion, and even in the case of the vinyl chloride decorative film ink. The remaining ink of 4 to 5 gradations was observed, and it was confirmed that good adhesion was obtained regardless of which ink was used.
Further, this film showed a crystal melting peak of 135 ° C. in the range of 70 to 170 ° C. and a crystal melting peak of 232 ° C. in the range of 200 ° C. or higher. The temperature of this film when stretched by 1500 μm was 134 ° C. Furthermore, it was confirmed that the storage elastic modulus (E') at 190 ° C. was 3.0 × ¹⁰⁶ Pa, and that a sufficient elastic modulus was maintained even at around 200 ° C. and the shape was maintained.
As shown above, excellent appearance, good adhesion to ink, desired crystal melting peak in the range of 70-170 ° C and above 200 ° C, sufficient film elongation in the range of 80-165 ° C and 190. Since it has a sufficient storage elastic modulus at ° C, a film having both the required performance and appearance was obtained.

[Example 2]
Polymethylpentene (A) and random polypropylene were used as the blending amounts in Table 1.
The thickness configuration was the same as in Example 1 except that the rotation speed of each extruder was set so as to be 2.3 μm / 145.4 μm / 2.3 μm (150 μm in total for each layer).
No foreign matter or streak-like defects were found in this film, and the film had an excellent appearance.
It was confirmed that the tensile elastic modulus was 870 MPa and the tensile elongation at break was 500%, and that it had sufficient flexibility and fracture characteristics.
Regarding the adhesion of the ink provided on the surface layer side of this film, in the case of the olefin-based building material film ink, no peeling was observed in all 6 gradations, showing excellent adhesion, and even in the case of the vinyl chloride decorative film ink. The remaining ink of 4 to 5 gradations was observed, and it was confirmed that good adhesion was obtained regardless of which ink was used.
Further, this film showed a crystal melting peak of 135 ° C. in the range of 70 to 170 ° C. and a crystal melting peak of 232 ° C. in the range of 200 ° C. or higher. The temperature of this film when stretched by 1500 μm was 135 ° C. Furthermore, it was confirmed that the storage elastic modulus (E') at 190 ° C. was 3.1 × ¹⁰⁶ Pa, and that a sufficient elastic modulus was maintained even at around 200 ° C. and the shape was maintained.
As shown above, excellent appearance, good adhesion to ink, desired crystal melting peak in the range of 70-170 ° C and above 200 ° C, sufficient film elongation in the range of 80-165 ° C and 190. Since it has a sufficient storage elastic modulus at ° C, a film having both the required performance and appearance was obtained.

[Example 3]
It was carried out in the same manner as in Example 1 except that polymethylpentene (A), random polypropylene and homopolypropylene were used as shown in Table 1.
No foreign matter or streak-like defects were found in this film, and the film had an excellent appearance.
It was confirmed that the tensile elastic modulus was 900 MPa and the tensile elongation at break was 500%, and that it had sufficient flexibility and fracture characteristics.
Regarding the adhesion of the ink provided on the surface layer side of this film, in the case of the olefin-based building material film ink, no peeling was observed in all 6 gradations, showing excellent adhesion, and even in the case of the vinyl chloride decorative film ink. The remaining ink of 4 to 5 gradations was observed, and it was confirmed that good adhesion was obtained regardless of which ink was used.
Further, this film showed crystal melting peaks of 132 ° C. and 158 ° C. in the range of 70 to 170 ° C., and a crystal melting peak of 232 ° C. in the range of 200 ° C. or higher. The temperature of this film when stretched by 1500 μm was 135 ° C. Furthermore, it was confirmed that the storage elastic modulus (E') at 190 ° C. was 3.1 × ¹⁰⁶ Pa, and that a sufficient elastic modulus was maintained even at around 200 ° C. and the shape was maintained.
As shown above, excellent appearance, good adhesion to ink, desired crystal melting peak in the range of 70-170 ° C and above 200 ° C, sufficient film elongation in the range of 80-165 ° C and 190. Since it has a sufficient storage elastic modulus at ° C, a film having both the required performance and appearance was obtained.

[Example 4]
It was carried out in the same manner as in Example 1 except that polymethylpentene (A), random polypropylene and an olefin-based elastomer were used as shown in Table 1.
No foreign matter or streak-like defects were found in this film, and the film had an excellent appearance.
It was confirmed that the tensile elastic modulus was 860 MPa and the tensile elongation at break was 510%, and that the product had sufficient flexibility and fracture characteristics.
Regarding the adhesion of the ink provided on the surface layer side of this film, in the case of the olefin-based building material film ink, no peeling was observed in all 6 gradations, showing excellent adhesion, and even in the case of the vinyl chloride decorative film ink. The remaining ink of 4 to 5 gradations was observed, and it was confirmed that good adhesion was obtained regardless of which ink was used.
Further, this film showed a crystal melting peak of 132 ° C. in the range of 70 to 170 ° C. and a crystal melting peak of 232 ° C. in the range of 200 ° C. or higher. The temperature of this film when stretched by 1500 μm was 134 ° C. Furthermore, it was confirmed that the storage elastic modulus (E') at 190 ° C. was 3.0 × ¹⁰⁶ Pa, and that a sufficient elastic modulus was maintained even at around 200 ° C. and the shape was maintained.
As shown above, excellent appearance, good adhesion to ink, desired crystal melting peak in the range of 70-170 ° C and above 200 ° C, sufficient film elongation in the range of 80-165 ° C and 190. Since it has a sufficient storage elastic modulus at ° C, a film having both the required performance and appearance was obtained.

[Example 5]
It was carried out in the same manner as in Example 1 except that polymethylpentene (A) and random polypropylene were used as shown in Table 1.
No foreign matter or streak-like defects were found in this film, and the film had an excellent appearance.
It was confirmed that the tensile elastic modulus was 880 MPa and the tensile elongation at break was 460%, and that it had sufficient flexibility and fracture characteristics.
Regarding the adhesion of the ink provided on the surface layer side of this film, in the case of the olefin-based building material film ink, no peeling was observed in all 6 gradations, showing excellent adhesion, and even in the case of the vinyl chloride decorative film ink. The remaining ink of 4 to 5 gradations was observed, and it was confirmed that good adhesion was obtained regardless of which ink was used.
Further, this film showed a crystal melting peak of 135 ° C. in the range of 70 to 170 ° C., and a crystal melting peak of 231 ° C. in the range of 200 ° C. or higher. The temperature of this film when stretched by 1500 μm was 138 ° C. Furthermore, it was confirmed that the storage elastic modulus (E') at 190 ° C. was 3.2 × ¹⁰⁶ Pa, and that a sufficient elastic modulus was maintained even at around 200 ° C. and the shape was maintained.
As shown above, excellent appearance, good adhesion to ink, desired crystal melting peak in the range of 70-170 ° C and above 200 ° C, sufficient film elongation in the range of 80-165 ° C and 190. Since it has a sufficient storage elastic modulus at ° C, a film having both the required performance and appearance was obtained.

[Example 6]
It was carried out in the same manner as in Example 1 except that polymethylpentene (A), random polypropylene and homopolypropylene were used as shown in Table 1.
Although foreign matter and streaky defects were slightly observed in this film, it was usable and had a good appearance. It was confirmed that the tensile elastic modulus was 1000 MPa and the tensile elongation at break was 420%, and that it had sufficient flexibility and fracture characteristics.
Regarding the adhesion of the ink provided on the surface layer side of this film, in the case of the olefin-based building material film ink, no peeling was observed in all 6 gradations, showing excellent adhesion, and even in the case of the vinyl chloride decorative film ink. The remaining ink of 4 to 5 gradations was observed, and it was confirmed that good adhesion was obtained regardless of which ink was used.
Further, this film showed crystal melting peaks of 135 ° C. and 158 ° C. in the range of 70 to 170 ° C., and a crystal melting peak of 232 ° C. in the range of 200 ° C. or higher. The temperature of this film when stretched by 1500 μm was 160 ° C. Furthermore, it was confirmed that the storage elastic modulus (E') at 190 ° C. was 3.7 × ¹⁰⁶ Pa, and that a sufficient elastic modulus was maintained even at around 200 ° C. and the shape was maintained.
As shown above, excellent appearance, good adhesion to ink, desired crystal melting peak in the range of 70-170 ° C and above 200 ° C, sufficient film elongation in the range of 80-165 ° C and 190. Since it has a sufficient storage elastic modulus at ° C, a film having both the required performance and appearance was obtained.

[Example 7]
Polymethylpentene (A) and random polypropylene were used as shown in Table 1, and the same procedure as in Example 1 was carried out except that the back layer also contained polymethylpentene (A).
No foreign matter or streak-like defects were found in this film, and the film had an excellent appearance.
It was confirmed that the tensile elastic modulus was 900 MPa and the tensile elongation at break was 500%, and that it had sufficient flexibility and fracture characteristics.
Regarding the adhesion of the ink provided on the surface layer side of this film, in the case of the olefin-based building material film ink, no peeling was observed in all 6 gradations, showing excellent adhesion, and even in the case of the vinyl chloride decorative film ink. The remaining ink of 4 to 5 gradations was observed, and it was confirmed that good adhesion was obtained regardless of which ink was used.
Further, this film showed a crystal melting peak of 132 ° C. in the range of 70 to 170 ° C. and a crystal melting peak of 232 ° C. in the range of 200 ° C. or higher. The temperature of this film when stretched by 1500 μm was 140 ° C. Furthermore, it was confirmed that the storage elastic modulus (E') at 190 ° C. was 3.1 × ¹⁰⁶ Pa, and that a sufficient elastic modulus was maintained even at around 200 ° C. and the shape was maintained.
As shown above, excellent appearance, good adhesion to ink, desired crystal melting peak in the range of 70-170 ° C and above 200 ° C, sufficient film elongation in the range of 80-165 ° C and 190. Since it has a sufficient storage elastic modulus at ° C, a film having both the required performance and appearance was obtained.

[Example 8]
It was carried out in the same manner as in Example 1 except that polymethylpentene (B) and random polypropylene were used as shown in Table 1.
No foreign matter or streak-like defects were found in this film, and the film had an excellent appearance.
It was confirmed that the tensile elastic modulus was 600 MPa and the tensile elongation at break was 520%, and that it had sufficient flexibility and fracture characteristics.
Regarding the adhesion of the ink provided on the surface layer side of this film, in the case of the olefin-based building material film ink, no peeling was observed in all 6 gradations, showing excellent adhesion, and even in the case of the vinyl chloride decorative film ink. The remaining ink of 4 to 5 gradations was observed, and it was confirmed that good adhesion was obtained regardless of which ink was used.
Further, this film showed a crystal melting peak of 135 ° C. in the range of 70 to 170 ° C. and a crystal melting peak of 224 ° C. in the range of 200 ° C. or higher. The temperature of this film when stretched by 1500 μm was 130 ° C. Furthermore, it was confirmed that the storage elastic modulus (E') at 190 ° C. was 1.3 × ¹⁰⁶ Pa, and that a sufficient elastic modulus was maintained even at around 200 ° C. and the shape was maintained.
As shown above, excellent appearance, good adhesion to ink, desired crystal melting peak in the range of 70-170 ° C and above 200 ° C, sufficient film elongation in the range of 80-165 ° C and 190. Since it has a sufficient storage elastic modulus at ° C, a film having both the required performance and appearance was obtained.

[Example 9]
Polymethylpentene (A) and random polypropylene were used as shown in Table 1, and the same procedure as in Example 1 was carried out except that the surface layer also contained 10% by mass of polymethylpentene (A).
No foreign matter or streak-like defects were found in this film, and the film had an excellent appearance.
It was confirmed that the tensile elastic modulus was 900 MPa and the tensile elongation at break was 500%, and that it had sufficient flexibility and fracture characteristics.
However, regarding the adhesion of the ink provided on the surface layer side of this film, in the case of the olefin-based building material film ink, peeling was not seen in all 6 gradations and excellent adhesion was shown, but the ink for vinyl chloride decorative film. In the case of, only 2 to 3 gradations of ink remained, and since the surface layer contained a polymethylpentene-based resin, the adhesion was slightly inferior depending on the type of ink.
Further, this film showed a crystal melting peak of 132 ° C. in the range of 70 to 170 ° C. and a crystal melting peak of 232 ° C. in the range of 200 ° C. or higher. The temperature of this film when stretched by 1500 μm was 134 ° C. Furthermore, it was confirmed that the storage elastic modulus (E') at 190 ° C. was 3.2 × ¹⁰⁶ Pa, and that a sufficient elastic modulus was maintained even at around 200 ° C. and the shape was maintained.
As shown above, excellent appearance, good adhesion to the ink, desired crystal melting peaks in the 70-170 ° C range and above 200 ° C, sufficient film elongation in the 80-165 ° C range and 190. Since it has a sufficient storage elastic modulus at ° C, a film having both the required performance and appearance was obtained.

[Example 10]
It was carried out in the same manner as in Example 1 except that polymethylpentene (A) and random polypropylene were used as shown in Table 1.
Since this film contained a large amount of polymethylpentene-based resin, foreign matter and streak-like defects caused by the resin were observed, and the film was inferior in appearance. Since the tensile elastic modulus was 1420 MPa and the tensile elongation at break was 350%, it is assumed that the film is inferior in processability due to its high elastic modulus.
Regarding the adhesion of the ink provided on the surface layer side of this film, in the case of the olefin-based building material film ink, no peeling was observed in all 6 gradations, showing excellent adhesion, and even in the case of the vinyl chloride decorative film ink. The remaining ink of 4 to 5 gradations was observed, and it was confirmed that good adhesion was obtained regardless of which ink was used.
Further, this film showed a crystal melting peak of 132 ° C. in the range of 70 to 170 ° C. and a crystal melting peak of 232 ° C. in the range of 200 ° C. or higher.
Further, the temperature of this film at the time of extension of 1500 μm is 190 ° C., and it is presumed that the processing temperature range of the film is high and the processability is inferior.
The storage elastic modulus (E') at 190 ° C. was 4.2 × ¹⁰⁶ Pa, and it was confirmed that a sufficient elastic modulus was maintained even at around 200 ° C. and the shape was maintained.
As shown above, it is presumed that the appearance is inferior due to the large amount of polymethylpentene resin, the elastic modulus is high, and the processability is inferior due to the high temperature at the time of extension of 1500 μm, but the storage elastic modulus at 190 ° C. is sufficient. Therefore, a film having excellent heat resistance and sufficient adhesion to ink was obtained.

[Example 11]
The same procedure as in Example 1 was carried out except that polymethylpentene (B), random polypropylene, an olefin elastomer and a styrene elastomer (A) were used as shown in Table 1.
No foreign matter or streak-like defects were found in this film, and the film had an excellent appearance.
It was confirmed that the tensile elastic modulus was 380 MPa and the tensile elongation at break was 470%, and that it had sufficient flexibility and fracture characteristics.
Regarding the adhesion of the ink provided on the surface layer side of this film, in the case of the olefin-based building material film ink, no peeling was observed in all 6 gradations, showing excellent adhesion, and even in the case of the vinyl chloride decorative film ink. The remaining ink of 4 to 5 gradations was observed, and it was confirmed that good adhesion was obtained regardless of which ink was used.
Further, this film showed a crystal melting peak of 135 ° C. in the range of 70 to 170 ° C. and a crystal melting peak of 224 ° C. in the range of 200 ° C. or higher. The temperature of this film when stretched by 1500 μm was 124 ° C. Furthermore, it was confirmed that the storage elastic modulus (E') at 190 ° C. was ^8.5 × 105 Pa, and that a sufficient elastic modulus was maintained even at around 200 ° C. and the shape was maintained.
As shown above, excellent appearance, good adhesion to ink, desired crystal melting peak in the range of 70-170 ° C and above 200 ° C, sufficient film elongation in the range of 80-165 ° C and 190. Since it has a sufficient storage elastic modulus at ° C, a film having both the required performance and appearance was obtained.

[Example 12]
The same procedure as in Example 1 was carried out except that polymethylpentene (A), random polypropylene, an olefin elastomer and a styrene elastomer (A) were used as shown in Table 1.
No foreign matter or streak-like defects were found in this film, and the film had an excellent appearance.
It was confirmed that the tensile elastic modulus was 560 MPa and the tensile elongation at break was 480%, and that it had sufficient flexibility and fracture characteristics.
Regarding the adhesion of the ink provided on the surface layer side of this film, in the case of the olefin-based building material film ink, no peeling was observed in all 6 gradations, showing excellent adhesion, and even in the case of the vinyl chloride decorative film ink. The remaining ink of 4 to 5 gradations was observed, and it was confirmed that good adhesion was obtained regardless of which ink was used.
Further, this film showed a crystal melting peak of 134 ° C. in the range of 70 to 170 ° C. and a crystal melting peak of 232 ° C. in the range of 200 ° C. or higher. The temperature of this film when stretched by 1500 μm was 133 ° C. Furthermore, it was confirmed that the storage elastic modulus (E') at 190 ° C. was 3.4 × ¹⁰⁶ Pa, and that a sufficient elastic modulus was maintained even at around 200 ° C. and the shape was maintained.
As shown above, excellent appearance, good adhesion to ink, desired crystal melting peak in the range of 70-170 ° C and above 200 ° C, sufficient film elongation in the range of 80-165 ° C and 190. Since it has a sufficient storage elastic modulus at ° C, a film having both the required performance and appearance was obtained.

[Example 13]
The same procedure as in Example 2 was carried out except that polymethylpentene (A), random polypropylene, an olefin elastomer and a styrene elastomer (B) were used as shown in Table 1.
No foreign matter or streak-like defects were found in this film, and the film had an excellent appearance.
It was confirmed that the tensile elastic modulus was 460 MPa and the tensile elongation at break was 520%, and that it had sufficient flexibility and fracture characteristics.
Regarding the adhesion of the ink provided on the surface layer side of this film, in the case of the olefin-based building material film ink, no peeling was observed in all 6 gradations, showing excellent adhesion, and even in the case of the vinyl chloride decorative film ink. The remaining ink of 4 to 5 gradations was observed, and it was confirmed that good adhesion was obtained regardless of which ink was used.
Further, this film showed a crystal melting peak of 132 ° C. in the range of 70 to 170 ° C. and a crystal melting peak of 232 ° C. in the range of 200 ° C. or higher. The temperature of this film when stretched by 1500 μm was 128 ° C. Furthermore, it was confirmed that the storage elastic modulus (E') at 190 ° C. was 2.6 × ¹⁰⁶ Pa, and that a sufficient elastic modulus was maintained even at around 200 ° C. and the shape was maintained.
As shown above, excellent appearance, good adhesion to ink, desired crystal melting peak in the range of 70-170 ° C and above 200 ° C, sufficient film elongation in the range of 80-165 ° C and 190. Since it has a sufficient storage elastic modulus at ° C, a film having both the required performance and appearance was obtained.

[Example 14]
Polymethylpentene (A), random polypropylene, olefin elastomer and styrene elastomer (B) are blended in the amounts shown in Table 1, and the thickness composition is 22.5 μm / 105 μm / 22.5 μm (total of each layer is 150 μm). The procedure was carried out in the same manner as in Example 1 except that the rotation speed of each extruder was set.
No foreign matter or streak-like defects were found in this film, and the film had an excellent appearance.
It was confirmed that the tensile elastic modulus was 490 MPa and the tensile elongation at break was 510%, and that the product had sufficient flexibility and fracture characteristics.
Regarding the adhesion of the ink provided on the surface layer side of this film, in the case of the olefin-based building material film ink, no peeling was observed in all 6 gradations, showing excellent adhesion, and even in the case of the vinyl chloride decorative film ink. The remaining ink of 4 to 5 gradations was observed, and it was confirmed that good adhesion was obtained regardless of which ink was used.
Further, this film showed a crystal melting peak of 135 ° C. in the range of 70 to 170 ° C. and a crystal melting peak of 232 ° C. in the range of 200 ° C. or higher. The temperature of this film when stretched by 1500 μm was 129 ° C. Furthermore, it was confirmed that the storage elastic modulus (E') at 190 ° C. was 2.0 × ¹⁰⁶ Pa, and that a sufficient elastic modulus was maintained even at around 200 ° C. and the shape was maintained.
As shown above, excellent appearance, good adhesion to ink, desired crystal melting peak in the range of 70-170 ° C and above 200 ° C, sufficient film elongation in the range of 80-165 ° C and 190. Since it has a sufficient storage elastic modulus at ° C, a film having both the required performance and appearance was obtained.

[Example 15]
The same procedure as in Example 2 was carried out except that polymethylpentene (B), random polypropylene, an olefin elastomer and a styrene elastomer (A) were used as shown in Table 1.
No foreign matter or streak-like defects were found in this film, and the film had an excellent appearance.
It was confirmed that the tensile elastic modulus was 340 MPa and the tensile elongation at break was 470%, and that it had sufficient flexibility and fracture characteristics.
Regarding the adhesion of the ink provided on the surface layer side of this film, in the case of the olefin-based building material film ink, no peeling was observed in all 6 gradations, showing excellent adhesion, and even in the case of the vinyl chloride decorative film ink. The remaining ink of 4 to 5 gradations was observed, and it was confirmed that good adhesion was obtained regardless of which ink was used.
Further, this film showed a crystal melting peak of 132 ° C. in the range of 70 to 170 ° C. and a crystal melting peak of 224 ° C. in the range of 200 ° C. or higher. The temperature of this film when stretched by 1500 μm was 117 ° C. Furthermore, it was confirmed that the storage elastic modulus (E') at 190 ° C. was 1.1 × ¹⁰⁶ Pa, and that a sufficient elastic modulus was maintained even at around 200 ° C. and the shape was maintained.
As shown above, excellent appearance, good adhesion to ink, desired crystal melting peak in the range of 70-170 ° C and above 200 ° C, sufficient film elongation in the range of 80-165 ° C and 190. Since it has a sufficient storage elastic modulus at ° C, a film having both the required performance and appearance was obtained.

[Comparative Example 1]
Polymethylpentene (A) and random polypropylene were used as shown in Table 1, and the same procedure as in Example 1 was carried out except that the surface layer also contained 30% by mass of polymethylpentene (A).
No foreign matter or streak-like defects were found in this film, and the film had a good appearance. However, when the adhesion of the ink provided on the surface layer side of this film was confirmed, it was found that the ink for olefin-based building material film was used. Although peeling was not seen in all 6 gradations and excellent adhesion was shown, in the case of the ink for vinyl chloride decorative film, only one gradation or less of the ink remained, and a lot of polymethylpentene resin was used. When it was included, the adhesion was significantly inferior depending on the type of ink.

[Comparative Example 2]
Polymethylpentene (A) and random polypropylene were used as shown in Table 1, and the same procedure as in Example 1 was carried out except that the surface layer also contained 80% by mass of polymethylpentene (A).
Since the surface layer of this film contained a large amount of polymethylpentene-based resin, foreign matter and streak-like defects caused by the resin were observed, and the film was inferior in appearance.
When the adhesion of the ink provided on the surface layer side of this film was confirmed, in both the olefin-based building material film ink and the vinyl chloride decorative film ink, only one gradation or less of the ink remained, and the surface layer. When a large amount of polymethylpentene-based resin was contained in the ink, the adhesion was significantly inferior regardless of the type of ink.

[Comparative Example 3]
It was carried out in the same manner as in Example 1 except that polymethylpentene (A) and random polypropylene were used as shown in Table 1.
No foreign matter or streak-like defects were found in this film, and the film had an excellent appearance.
It was confirmed that the tensile elastic modulus was 620 MPa and the tensile elongation at break was 590%, and that it had sufficient flexibility and fracture characteristics.
Regarding the adhesion of the ink provided on the surface layer side of this film, in the case of the olefin-based building material film ink, no peeling was observed in all 6 gradations, showing excellent adhesion, and even in the case of the vinyl chloride decorative film ink. The remaining ink of 4 to 5 gradations was observed, and it was confirmed that good adhesion was obtained regardless of which ink was used.
Further, this film showed a crystal melting peak of 135 ° C. in the range of 70 to 170 ° C., and a crystal melting peak of 231 ° C. in the range of 200 ° C. or higher. Also, 1 of this film
The temperature at the time of extension of 500 μm was 122 ° C.
However, since the film melted at 152 ° C., the storage elastic modulus (E') at 190 ° C. could not be measured, and it was confirmed that it was difficult to maintain the film shape at around 200 ° C.
As shown above, although it has a melting point of 200 ° C. or higher, it is inferior in heat resistance due to the low content of polymethylpentene.

[Comparative Example 4]
It was carried out in the same manner as in Example 1 except that only random polypropylene was used.
No foreign matter or streak-like defects were found in this film, and the film had an excellent appearance.
It was confirmed that the tensile elastic modulus was 500 MPa and the tensile elongation at break was 750%, and that it had sufficient flexibility and fracture characteristics.
Regarding the adhesion of the ink provided on the surface layer side of this film, in the case of the olefin-based building material film ink, no peeling was observed in all 6 gradations, showing excellent adhesion, and even in the case of the vinyl chloride decorative film ink. The remaining ink of 4 to 5 gradations was observed, and it was confirmed that good adhesion was obtained regardless of which ink was used.
Furthermore, although this film showed a crystal melting peak at 135 ° C in the range of 70 to 170 ° C, no crystal melting peak was observed in the range of 200 ° C or higher because it did not contain a polymethylpentene resin. .. The temperature of this film at the time of extension of 1500 μm was 120 ° C., but since the film was melted at 140 ° C. because it did not contain polymethylpentene resin, the storage elastic modulus at 190 ° C. (E). ') Could not be measured, and it was confirmed that it was difficult to maintain the film shape at around 200 ° C.
As shown above, it was inferior in heat resistance because it did not have a melting point of 200 ° C. or higher.

[Comparative Example 5]
The procedure was the same as in Example 1 except that random polypropylene and a polyamide grafted polyolefin resin were used as the blending amounts as shown in Table 1.
It is presumed that the compatibility between the random polypropylene and the polyamide-grafted polyolefin resin was not sufficient, and foreign matter and streaky defects were noticeably observed in this film, so the film may be significantly inferior in appearance. confirmed.

[Example 16]
Acrylic adhesive (SK Dyne 1502C manufactured by Soken Chemical Co., Ltd.) is applied on the separator by the comma coating method so that the thickness of the adhesive layer after drying is 25 μm, and it is put into a hot air dryer at 80 ° C. After drying for 5 minutes, an adhesive layer was formed.
The separator having the pressure-sensitive adhesive layer was attached to the surface of the film obtained in Example 1 on the surface layer side to obtain a pressure-sensitive adhesive film having the film and the pressure-sensitive adhesive layer.

[Example 17]
Acrylic adhesive (SK Dyne 1502C manufactured by Soken Chemical Co., Ltd.) is applied on the separator by the comma coating method so that the thickness of the adhesive layer after drying is 25 μm, and it is put into a hot air dryer at 80 ° C. After drying for 5 minutes, an adhesive layer was formed.
By adhering the separator having the pressure-sensitive adhesive layer to the surface on the print layer side of the film on which the ink for the olefin-based building material film prepared in Example 1 is laminated, a cosmetic pressure-sensitive adhesive film having the print layer and the pressure-sensitive adhesive layer can be obtained. Obtained.

[Industrial applicability]
By using the thermoplastic resin film of the present invention, it is possible to obtain a film having good processability, handleability, heat resistance, excellent appearance according to the application, and adhesion to a printing layer, an adhesive layer, etc. Can be done. Further, it is also possible to obtain an adhesive film, a decorative film or a cosmetic adhesive film by laminating an adhesive layer or a printing layer on the film, and these films can be used for semiconductor manufacturing processes, automobile interior / exterior and their cosmetic applications. Can also be suitably used.

Claims (12)

In differential scanning calorimetry, it has at least one crystal melting peak in the temperature range of 70 ° C. or higher and 170 ° C. or lower, and further has a crystal melting peak in the temperature range of 200 ° C. or higher, in 100% by mass of the thermoplastic resin. It is characterized by having a surface layer containing 0 to 20% by mass of the polymethylpentene resin and having a layer containing 20 to 90% by mass of the polymethylpentene resin in 100% by mass of the thermoplastic resin. Thermoplastic resin film. The thermoplastic resin film according to claim 1, wherein the tensile elastic modulus is 1400 MPa or less. The thermoplastic resin film according to claim 1 or 2, which comprises a thermoplastic resin having at least one crystal melting peak in the temperature range of 70 ° C. or higher and 150 ° C. or lower in the differential scanning calorimetry. The thermoplastic resin film according to any one of claims 1 to 3, wherein any one or more of a polyolefin resin and a styrene elastomer is used as the thermoplastic resin other than the polymethylpentene resin. .. The thermoplastic resin film according to claim 4, wherein the polyolefin-based resin contains at least one selected from the group consisting of polypropylene-based resins and olefin-based elastomers. The thermoplastic according to any one of claims 1 to 5, wherein the film exhibits an elongation of 1500 μm in the range of 80 to 165 ° C. when thermomechanical analysis is performed under the following conditions. Resin film.
<Conditions>
Specimen size: width 4 mm x length 20 mm
Distance between chucks: 8 mm
Measurement atmosphere: Under nitrogen atmosphere (nitrogen flow rate 100 ml / min)
Temperature rise rate: 5 ° C / min (start temperature: 23 ° C, end temperature: 250 ° C)
Load: 0.3N / mm ² The thermoplastic resin film according to any one of claims 1 to 6, wherein the storage elastic modulus E'at a vibration frequency of 1 Hz and a temperature of 190 ° C. is 1.0 × ¹⁰⁵ Pa or more. The thermoplastic resin film according to any one of claims 1 to 7, wherein the surface layer has a thickness of 2.0 μm or more. An adhesive film obtained by laminating an adhesive layer on the surface of the thermoplastic resin film according to any one of claims 1 to 8. The adhesive film according to claim 9, which is used as a film for a semiconductor manufacturing process. A decorative film formed by laminating a printing layer on the surface of the thermoplastic resin film according to any one of claims 1 to 8. A cosmetic adhesive film obtained by further laminating an adhesive layer on the print layer side of the decorative film according to claim 11.